JP2782909B2 - Photopolymerizable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is obtained by irradiating an actinic ray such as an ultraviolet ray or a visible ray with a photopolymerizable resin composition which is polymerized and cured, and obtained by photopolymerizing the composition. About resin.

<Prior Art> Conventionally, vulcanized synthetic rubber, acrylic rubber, silicone rubber, and the like have been known as elastic polymer materials. Further, as photopolymerizable polymer materials having elasticity, acryl-modified silicone resins (JP-A-62-119216), urethane-modified acrylic resins (JP-A-60-163911) and the like are known.

However, the silicone rubber has problems in mechanical strength, cost, adhesion to other materials, and the like, and vulcanized synthetic rubber and acrylic rubber have disadvantages in that a molding process such as a vulcanization operation is complicated. is there.

<Problems to be Solved by the Invention> An object of the present invention is to provide a resin having a desired viscoelasticity, in which the molding step is easy, and which is excellent in aging resistance and surface state by performing photopolymerization, and is excellent. An object of the present invention is to provide a photopolymerizable resin composition.

Another object of the present invention is excellent in aging resistance and surface condition,
Moreover, it is to provide a resin having a desired viscoelasticity.

<Means for Solving the Problems> According to the present invention, the following general formula (I) (Wherein, R ₁ is an acryloyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group,
Represents a vinylbenzyl group or an allyl group, and R ₂ has 1 to 1 carbon atoms
8 represents an alkyl group, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ₃ represents a hydrogen atom or a methyl group.
N represents an integer of 1 to 50) and a monofunctional monomer represented by the following general formula (II): (Wherein, R ₄ and R ₅ represent an acryloyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group, a vinylbenzyl group or an allyl group, and R ₆ represents a hydrogen atom or a methyl group. Represents an integer of 1 to 50), and a homopolymer of a bifunctional monomer represented by the general formula (I) and / or
A chain copolymer obtained by copolymerizing a functional monomer and other ethylenically unsaturated monomers, and a photopolymerization initiator as essential components, and the blending ratio of the essential components is as described above. With respect to 100 parts by weight of the monofunctional monomer represented by the formula (I), 0.01 to 30 parts by weight of the bifunctional monomer, 10 to 300 parts by weight of the homopolymer and / or copolymer, and the photopolymerization There is provided a photopolymerizable resin composition characterized in that the initiator is 0.01 to 10 parts by weight.

 Hereinafter, the present invention will be described in more detail.

The photopolymerizable resin composition of the present invention has a specific monofunctional monomer, a specific bifunctional monomer, a specific polymer and / or copolymer and a photopolymerization initiator as essential components, It is characterized by containing the essential components in a specific blending ratio.

The monofunctional monomer used in the present invention can be represented by the following general formula (I): In the formula, R ₁ is an acryloyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group,
A vinylbenzyl group or an allyl group, R ₂ is a hydrogen atom,
It represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ₃ represents a hydrogen atom or a methyl group. N represents an integer of 1 to 50. When R ₂ is an alkyl group having 9 or more carbon atoms or a cycloalkyl group, production is difficult. Also, when n exceeds 50, production is difficult. Examples of the monofunctional monomer represented by the general formula (I) include methoxyethyloxy (meth) acrylate, phenoxyethyloxy (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and isobutoxytetraethylene glycol (meth) acrylate. , Methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol monomalate, methoxypolyethylene glycol bismalate, methoxypolyethylene glycol monofumarate, methoxypolyethylene glycol bisfumarate, methoxypolyethylene glycol monoitaconate, methoxypolyethylene glycol bisitaconate, ethoxy Polyethylene glycol (meth) acrylate, isopropoxy polyethylene glycol Meth)
Acrylate, isobutoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol vinyl ether, phenoxy polyethylene glycol vinyl ether, methoxy polyethylene glycol vinyl benzyl ether, methoxy ethylene glycol allyl ether, phenoxy polyethylene glycol allyl ether, methoxypropyl Oxy (meth) acrylate, phenoxypropyloxy (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobutoxytetrapropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolypropylene glycol monomalate, Alkoxy polypropylene glycol bismuth rate, methoxy polypropylene glycol mono fumarate, methoxy polypropylene glycol bis fumarate, methoxy polypropylene glycol mono itaconate, methoxy polypropylene glycol bis itaconate, ethoxy polypropylene glycol (meth)
Acrylate, isopropoxy polypropylene glycol (meth) acrylate, isobutoxy polypropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, methoxy polypropylene glycol vinyl ether, phenoxy polypropylene glycol vinyl ether, methoxy polypropylene glycol vinyl benzyl ether, methoxy propylene glycol allyl ether And phenoxy polypropylene glycol allyl ether.

The bifunctional monomer used in the present invention can be represented by the following general formula (II): In the formula, R ₄ and R ₅ represent an acryloyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group, a vinylbenzyl group or an allyl group, and R ₆ represents a hydrogen atom or a methyl group. N represents an integer of 1 to 50. If n exceeds 50, manufacture is difficult.
As the bifunctional monomer represented by the general formula (II),
For example, ethyloxy di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bis (polyethylene glycol) malate, bis (polyethylene glycol)
Fumarate, bis (polyethylene glycol) itaconate, polyethylene glycol divinyl ether, polyethylene glycol bis (vinyl benzyl ether),
Ethylene glycol diallyl ether, polyethylene glycol diallyl ether, propyloxydi (meth)
Acrylate, dipropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bis (polypropylene glycol) malate,
Bis (polypropylene glycol) fumarate, bis (polypropylene glycol) itaconate, polypropylene glycol bis (vinyl benzyl ether), propylene glycol diallyl ether, polypropylene glycol diallyl ether and the like can be mentioned.

In the present invention, the monofunctional monomer or the bifunctional monomer can be synthesized by applying, for example, an esterification reaction, a vinylation, a start reaction or a termination reaction of living polymerization of ethylene oxide or propylene oxide, or the like.

The polymer and / or copolymer used in the present invention is
A homopolymer of the monofunctional monomer and / or a copolymer of the monofunctional monomer and another ethylenically unsaturated monomer. The molecular weight of the homopolymer and / or copolymer is 1000
The content of the monofunctional monomer in the copolymer is at least 20% by weight or more, preferably 30% by weight or more in the copolymer component. Is desirable. The ethylenically unsaturated monomer as the copolymer component may be any copolymer as long as it can be copolymerized with the monofunctional monomer. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Preferred examples thereof include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylates, vinyl ethers, vinyl acetate, styrene, and derivatives thereof.

The homopolymer or copolymer can be prepared, for example, by polymerization in a solvent or in the absence of a solvent in the presence of a suitable radical polymerization initiator. Examples of the radical polymerization initiator include various organic peroxides,
Examples include azo compounds, persulfates, perhalates, and redox reagents. Also, for example, light, oxygen,
The polymerization can also be initiated using radiation, plasma or the like. Further, the polymerization can be performed by a known bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method, or the like.

The photopolymerization initiator used in the present invention is not particularly limited, and a known photopolymerization initiator can be used.
Specifically, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, carbonyl compounds such as benzyl, benzophenone, acetophenone, and Michler's ketone; azo compounds such as azobisisobutyronitrile and azodibenzoyl; Examples thereof include sulfur compounds such as thiazolyl sulfide and tetraethylthiuram disulfide, halogen compounds such as carbon tetrabromide and tribromophenylsulfone, and 1,2-benzanthraquinone. In addition, especially wavelength 350
When photopolymerization is performed using light having a wavelength of up to 450 nm, a benzophenone group-containing polyvalent peroxyester represented by the following general formula (III) can be used.

Wherein R ₇ and R ₇ 'represents a tertiary alkyl group or a 3 aralkyl group having a carbon number of 9-12, respectively 4 to 8 carbon atoms, R ₈ and
R ₈ 'represents respectively hydrogen atom, a third Araruokishi group of the third alkoxy group or a C 9-12 4 to 8 carbon atoms. Examples of the benzophenone group-containing polyvalent peroxyester represented by the general formula (III) include, for example, 3,3 ′, 4,4′-
Tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-hexylperoxycarbonyl ) Benzophenone, 3,3 ', 4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra-
(T-cumylperoxycarbonyl) benzophenone,
3,3 ', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyl-bis- (mono-t-butylperoxyphthalate), carbonyl-bis- (mono-t-hexylperoxyphthalate) And the like. Further, when the photopolymerization reaction is carried out using visible light having a wavelength of 400 nm or more, for example, a photopolymerization initiator obtained by combining an organic peroxide with a pyrylium salt or a thiopyrylium salt, represented by the general formula (III) Benzophenone group-containing polyvalent peroxyesters and α-diketones, and photopolymerization initiators obtained by combining α-diketones and reducing agents. The pyrylium salt or thiopyrylium salt can be represented by the following general formula (IV): In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphthyl group, an alkylphenyl group, an alkoxyphenyl group, and a hydroxyphenyl group. Group, a halophenyl group, a nitrophenyl group, an aminophenyl group, an alkylaminophenyl group, an alkylaminostyryl group, a nitro group, an amino group or a hydroxyl group,
X represents an oxygen atom or a sulfur atom, and Y represents an anionic functional group. Specifically, for example, 4- (4-butoxyphenyl) -2,6-bis (4-methoxyphenyl) pyrylium perchlorate, 4- (4-butoxyphenyl) -2,6
-Diphenylthiopyrylium fluoroborate, 4-
(4-butoxyphenyl) -2,6-bis (4-methoxyphenyl) thiopyrylium fluoroborate and the like. Examples of the organic peroxide include benzophenone represented by the general formula (III). Group-containing polyvalent peroxyesters, methyl ethyl ketone peroxide, acetylacetone peroxide, t-butylcumyl peroxide, acetyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, di-tert-butylperoxyisophthalate, tri-t -Butyl peroxy trimellitate. The mixing ratio of the pyrylium salt or thiopyrylium salt to the organic peroxide is preferably from 1: 1 to 1: 500. Examples of the α-diketones include, for example, acenaphthenequinone, 9,10-phenanthrenequinone, camphorquinone, and β-nautquinone, and examples of the reducing agent include amines and barbituric acid derivatives. be able to. The compounding ratio of the benzophenone group-containing polyvalent peroxyesters and α-diketone is preferably 1: 0.01 to 10, and the compounding ratio of the α-diketone and the reducing agent is 1: 0.01 to 10. Preferably it is.

In the present invention, the mixing ratio of the essential components is 0.01 to 30 parts by weight of a bifunctional monomer, 10 to 300 parts by weight of a homopolymer or a copolymer and 100 to 300 parts by weight of a monofunctional monomer and photopolymerization. The initiator ranges from 0.01 to 10 parts by weight. At this time, if the composition of the present invention is not prepared in each of the above mixing ratios, the respective functions cannot be sufficiently exhibited, and further, when photopolymerized,
Since the desired viscoelastic resin cannot be obtained, it is necessary to set the mixing ratio as described above.

In order to prepare the photopolymerizable resin composition of the present invention, the essential components may be mixed at a specific ratio, and at this time, known organic filler particles and / or inorganic filler particles may be contained as necessary. Can be. The filler may be spherical, fine powder, microplate, fiber, whisker, or may have an irregular shape. Further, in addition to the filler, if necessary, a polymerization inhibitor, an antioxidant, a stabilizer, a pigment, a dye, and the like can be appropriately added.

The resin of the present invention is a viscoelastic resin obtained by photopolymerizing the photopolymerizable resin composition. The resin having the viscoelasticity is a resin which deforms in response to an external force and which gradually restores its original shape when the external force is removed, for example, has a property like a skin. Examples will be described in more detail.

To prepare the resin of the present invention, the photopolymerizable resin composition, ultraviolet light, active light such as visible light, by selecting and irradiating according to the contained photopolymerization initiator, by photopolymerization Obtainable. At this time, as a light source, for example, a mercury lamp, a fluorescent lamp, a xenon lamp, a halogen lamp, a tungsten lamp, a laser or the like can be used.

<Effect of the Invention> Since the photopolymerizable resin composition of the present invention is cured by photopolymerization, the molding process can be simplified, and the obtained resin of the present invention has aging resistance and is transparent and has surface properties. It has excellent specific viscoelasticity, so it is suitable for adhesives, inks, coating materials such as optical fibers, sealing materials such as liquid crystal cells, shock absorbing materials, vibration absorbing materials, soundproofing materials, dental materials, medical materials, etc. Can be used.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.

Production Examples 1-4 Methoxydiethylene glycol monomethacrylate 66
2,2'-azobisisobutyronitrile 1 as a polymerization initiator in a composition ratio of 33 parts by weight of methyl methacrylate
Using 100 parts by weight of benzene as a solvent and a solvent, a copolymer was synthesized by a usual solution polymerization method. Then
Precipitation with petroleum ether gave a solid copolymer (1). The weight average molecular weight of the obtained copolymer (1) was 150,000. Hereinafter, 60 parts by weight of methyl methacrylate, 20 parts by weight of methoxypolyethylene glycol monomethacrylate (n = 9), 15 parts by weight of isobutoxydiethylene glycol monomethacrylate by the same method,
Copolymer (2) was synthesized at a composition ratio of 5 parts by weight of butyl methacrylate. The weight average molecular weight of the obtained copolymer (2) was 100,000. Further, copolymer (3) was synthesized with a composition ratio of 5 parts by weight of isobutoxyethyl acrylate, 43 parts by weight of methoxytetraethylene glycol methacrylate, 50 parts by weight of methyl methacrylate, and 2 parts by weight of 2-ethyl-hexyl methacrylate. The weight average molecular weight of the obtained copolymer (3) was 220,000. Further, methoxytetraethylene glycol methacrylate 48 parts by weight, phenoxy polyethylene glycol allyl ether (n = 9) 2 parts by weight, methyl methacrylate 45 parts by weight,
Copolymer (4) was synthesized at a composition ratio of 5 parts by weight of vinyl acetate. The weight average molecular weight of the obtained copolymer (4) is 130,000.
Met.

Examples 1 to 8 The components having the compositions and compounding ratios shown in Table 1 were mixed to prepare a photopolymerizable resin composition. Then, the obtained composition is
After filling into a Teflon frame of 25 mm x 25 mm x 3 mm, the top and bottom were sandwiched by PET film, and the resin was manufactured by irradiating light from the front and back for 10 minutes each with an irradiator having four halogen lamps (150 W). .

Next, the obtained resin was subjected to a viscoelasticity test and an aging resistance test according to the following methods. The transparency, smell, and surface properties of the obtained resin were also measured. The results are shown in Table 2, and the results of the viscoelasticity test are shown in the figure.

Viscoelasticity test The obtained resin was allowed to stand at a constant temperature of 37 ° C. for 10 minutes to be kept at a constant temperature, and then the creep of the specimen was measured using a creep meter under the following measurement conditions.

Load 150g Measurement time 120 seconds (60 seconds load; 60 seconds unloading) Plunger diameter 3mm Aging resistance test The obtained resin was alternately immersed in cold water of 4 ° C and warm water of 60 ° C for 1 minute each. This was repeated 400 times, and the viscoelasticity was measured in the same manner as in the viscoelasticity test. The evaluation was represented by ，, Δ, and ×, since the change in viscoelasticity before and after the test was small.

Comparative Examples 1 to 4 The components having the compositions and compounding ratios shown in Table 1 were mixed to prepare a photopolymerizable resin composition, and then photopolymerization was performed in the same manner as in Examples 1 to 8 to produce a resin. Each test and measurement were performed on the obtained resin in the same manner as in Examples 1 to 8. The results are shown in Table 2 and the figures (however, Comparative Examples 1 and 2 have the same viscoelasticity as the examples, and the drawings are omitted.) From the results of the examples and the comparative examples, the results of the present invention are shown. It has been found that the composition can provide a resin having a desired viscoelasticity without performing a complicated vulcanization operation. Also, unlike the elastic body of Comparative Example 3, the obtained resin has a desired viscoelasticity such that it easily deforms under a load and gradually recovers when the load is removed, and at the same time, has a bad smell and transparency. It was also found to be excellent in physical properties such as surface properties and aging resistance.

[Brief description of the drawings]

FIG. 1 is a chart showing the results of the viscoelasticity test of the resin produced in Example 1, FIG. 2 is a chart showing the results of the viscoelasticity test of the resin produced in Example 2, and FIG. Example 3
FIG. 4 is a chart showing the results of the viscoelasticity test of the resin produced in Example 4, FIG. 4 is a chart showing the results of the viscoelasticity test of the resin produced in Example 4, and FIG. FIG. 6 is a chart showing the results of the elasticity test, FIG. 6 is a chart showing the results of the viscoelasticity test of the resin produced in Example 6, and FIG.
FIG. 9 is a chart showing the results of the viscoelasticity test of the resin produced in Example 7, FIG. 8 is a chart showing the results of the viscoelasticity test of the resin produced in Example 8, and FIG. FIG. 10 is a chart showing the results of the viscoelasticity test of the resin produced in Comparative Example 4, and FIG.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/027 511 G03F 7/027 511 (56) References JP-A-53-75291 (JP, A) JP-A-60-11840 (JP, A) JP-A-50-8832 (JP, A) JP-A-53-106786 (JP, A) JP-A-50-139189 (JP, A) (58) Fields investigated (Int. Cl. ⁶⁾ , DB name) C08F 290/00-290/04 C08F 2/48-2/50 C08F 20/26 G03F 7/027 C08F 265/06

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein, R ₁ is an acryloyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group,
Represents a vinylbenzyl group or an allyl group, and R ₂ has 1 to 1 carbon atoms
8 represents an alkyl group, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ₃ represents a hydrogen atom or a methyl group.
And n represents an integer of 1 to 50), and a monofunctional monomer represented by the following general formula (II): (Wherein, R ₄ and R ₅ represent an acrylolyl group, a methacryloyl group, a maleoyl group, a fumaroyl group, an itaconoyl group, a vinyl group, a vinylbenzyl group or an allyl group, and R ₆ represents a hydrogen atom or a methyl group. Represents an integer of 1 to 50), and a homopolymer of the monofunctional monomer represented by the general formula (I) and / or the monofunctional monomer and other ethylene A chain copolymer obtained by copolymerizing a reactive unsaturated monomer and a photopolymerization initiator as essential components, and the blending ratio of the essential components is represented by the general formula (I). With respect to 100 parts by weight of the functional monomer, 0.01 to 30 parts by weight of the bifunctional monomer, 10 to 300 parts by weight of the homopolymer and / or copolymer, and 0.01 to 10 parts by weight of the photopolymerization initiator. A photopolymerizable resin composition comprising: